Process and apparatus for performing endothermic catalytic reactions in the gas phase



April 2, 1946. R wlTKlEwlcz A2,397,899

` PROCESS AND APPARATUS FOR PERFORMING ENDOTHERMIC CATALYTIG 'REACTIONS IN THE GAS PHASE Filed March 30, 1939 2 Sheets-Sheet 2 INVENTOR A Patented AprrZ, 1946 Aclaires).'sm'llas .PATENT ort-fics' I l assises .ING

THEBMIC CAIALYTIC HEAO- END() TIONSINTHEGABPHAS nomen Wimmer, Lwow, Ponsa: vence in une y Property custodian Alien This invention vrelates to surface reactions and more particularly to catalytically induced chemical reactions which occur with substantial conf version between heat and vchemical energy.

Chemical reactions between gases or vapors v occur very often with endo-thermic edects. In

application Maren so. 1939. seran no. 234.995

stantially at constant temperatures thus prev venting mechanical deterioration.

many cases these `effects are vvery yserious and.

cause dimculties in keeping the temperature of the reaction at the desired level.

drops and consequently also the rate of reaction drops; the reaction is not completed and sometimes even changes the desired trend.

The apparatus usedv at present for endociples Aby which the heat is delivered for the rejaction. The first type is .based on an .intermittent cycle of operation. A solid material, which heat supply is not satisfactory, the temperature usually serves also as a catalyst, is heateddirectly v by combustion gases to the desired temperature:

lyst lls a space separated from the heating medium by walls, to which it isclosely adjacent. Only this layer of the catalyst which is close to the heated wall receives enough heat; layers placed at further distances are at lower temperatures due to insumcient heat transfer into the catalyst mass.

One object `of the present invention is to provide an eihcient apparatus and process for performing endo-thermic catalytic reactions in the gas-phase, and wherein the temperature of re= action is controlled by efficient heat-exchange with substantially the entire surface of the cataiyst.

Another object is to provide an apparatus where the reacting gases can min freely and pass through a number of layers of the catalyst with'A out chanelling.

-tus the heat is delivered continuously. The cata Still another objectis to provide anapparatus" another object is to .provide an appar-sms siving high out-put per unit of catalyst used. thus permitting the economical use of relatively expensive catalysts and. if desired. a frequent Vusing acata lyst in relatively thin layers and effecting heat Y change ot catalyst.

These objects Iaccomplish by exchange by direct radiation to its surface at which reaction occurs. t f

The apparatus according to this invention is represented schematically in the accompanying drawings in which each of the Figures l, 2 and lil is a view in vertical section. more or less diagrammatic, of an apparatus embodying my invention adapted for endo-thermic catalytic reactions such as watergas production.

. The apparatus (Figure i) has a reaction chamber i separated by a wall 2 from the heating space I. The reaction chamber contains perforated trays placed at a-distance from each other.

On these trays is placed the catalyst in a rather thin layer I. At the bottom of the heating space 3 are placed burners l fed by liquid or gaseous fuel. The heating space is insulatedby an external insulating wall 6. Combustion gases may be used in -preheating steam or in preheating gases entering the reaction chamben'or in heating a. boiler. Gases for the reaction enter the reaction chamber l through a conduit 1 andleave through conduit 8 or they can be passed in reverse direction, counter-current to the dame. Reaction .gases may be used directly when hot ior further .processing crean serve as a preheating medium for incoming gas. lZlhe distances `between the trays and the thickness of the catalyst layers are suitably selected so that between the surface of the catalyst layer and the next upper tray there remains a. rather large free space. e thickness of the catalyst layer can varydepen primarily on the activity and thecatalyst. These and other factors iniiuencethe thickness ci the catalyst within a wide range. In moet cases the thickness of the catalyst layers will range from to 2 inches but these gures are cited only as examples. and it is uobvious that the thicmess can vary within wider figures and the; catalyst layerA can be thinner or thicker without de from the spirit ofthe invention.

Free spaces between catalyst layers are very important because these free spaces enable the heat to radiate from the heated walls of the chamber upon the surface of the catalyst and also to mix the gases of reaction. l Generally the free spaces of the reaction chamber should be much larger than the spaces occupied by the catalyst. y

1 The reaction chamber can have any suitable shape, e. g. a cylinder, a prism or a cone. Its

ers Il, depending upon the size of the apparawalls are made of steel, or a special heat-resist- Y ant alloy or refractory ceramic material, depending upon the required temperature of reaction. The walls of the chamber are heated externally by any suitable means, e. g., liquid or gaseous fuel, and serve to radiate the heat or to transmit radiant heat to the catalyst and the reacting gases.

When a material which is relatively impermeable to radiant heat is used, the wall of the chamber itself must be heated to a temperature at which it becomes a good radiant source well above the required temperature at the surface of the catalyst. If, however, a material is used which is highhw permeable to infra-red radiation, as for example silica or certain 'refractory glasses, etc., the wall of the reaction chamber may remain relatively cool, e. g., at the optimum reaction temperature'while transmitting radiant heat from a flame, hot gases or liquid or from a radiating body outside the chamber.

The main amount of heat is furnished by radiation from or through the hot wall to the catalyst surface directly or by reflexion. v Comparatively, only a negligible amount of heat is furnished to the inner zones of the catalyst by conductivity. 'This fact shows the advantage of using the catalyst in thin vlayers exposing a large irradiated surface. This way a uniform distribution `of heat in the catalyst mass, especially at the surface where it is required for the reaction, and high performance of the catalyst are obtained.

,The reaction chamber can also be shaped in another very advantageous form, namely. as an annular space between two concentric cylinders. The heating is done within the inner cylinder. The wall of the outer cylinder of the reaction chamber serves for heat reflexion and insulation purposes; or additional heat radiation may be supplied through the outer walls.l

'I'his form of apparatus permits the use of a ,central flame, avoiding difiiculties of shaping and regulating the burners around a cylindrical reaction chamber, and also further improves the thermal efciency of the apparatus. The analysis of the radiant-heat-transfer from an outer jacket (wall) to the catalystin an inner' chamber has shown that in the optimum case the amount of heattransferred from the external jacket to the catalyst trays is equal to that amount which could be radiated from the jacket to a parallel wall having a surface equal to the.

surface of the jacket and having a temperature equal to the temperature of the catalyst. 'I'his fact, resultingfrom the laws of 'radiant-heattransfer, constitutes a limitation on the eiiiciency of the apparatus described in the earlier part of the application as compared with an apparatus where the reaction space has an annular form and is heated from the interior.

In Figure 2 a diagrammatic form of the preferred apparatus is shown. The inner jacket 9 is heated from the interior by a single flame l0- which is easy to handle and regulate. This flame can be obtained by means of one or manyburntus. The apparatus has an outside wall l2 made. e. g., from ordinary sheet-iron and masonry work of ceramic insulatingA material. The catalyst is placed in layers or trays I3 in the annular reaction'space between the inner jacket 9 and the outer wall of the apparatus l2. The catalyst is heated by the radiation of the inner jacket, which radiates leither directly on the catalyst and/or by reflexion from, e. g., the outer wall. It can be noticed that the catalyst layer is in this case very thin and large empty spaces provide ample opportunity for radiation from or through the heated `wall 9 to all 'parts of the surface of the catalyst layer.

Reaction gases leave the reaction space by conduit I4 and in aheat-exchanger l5 serve to preheat gases for the reaction, which preheated gases then enter the reaction space by conduit i8. Any

gas-tight device, e. g., liquid seal or bellows, etc., can be used to take care of expansions or contractions of the radiating Jacket 9.

In this preferred shape of apparatus as shown a more intense heat transfer to the catalyst is attained by designing the outer wall and/or its heat insulating cover to reflect the major part of the heat back 4on the catalyst. In this 'way either higher temperature of the catalyst can be obtained or more gas per reaction-volume can be passed. By increase of the outer radius of the apparatus, while simultaneously maintaining the ratio of the radiating area of the inner Jacket to the irradiated area of the catalyst layer, the catalystcan be advantageously distributed in very thin layers, which assists in achieving uniform heating of its mass. y

In case of a gas fuel it is advantageous to use visible flame enabling a more uniform distribution of the temperature on the whole length of the apparatus.

As the heat transfer of the apparatus of my invention is` based on radiation it is especially suitable for endo-thermic reactions occurring at elevated temperatures, e. g., reactions of dehydrogenation or isomerization or the conversion of hydrocarbons and steam into water-gas mixtures. Natural gas or refinery cracking gases can be converted with" steam into water-gas. of high hydrogen-content, Also other gases like bluegas can have their methane component converted to a large extent to carbon-monoxide and hydrogen. Any catalystl or combinations thereof of one or more catalysts with promoters and carriers suitable for the contemplated reaction can be used in v this apparatus, e. g., iron, nickel, cobalt, copper,

in metallic form or oxides or natural ores or salts, alumina, compounds of chromium, thorium, silicium, cerium, vanadium, tungsten, zinc, tin, lead, cadmium, manganese, molybdenum, sodium, potassium and boron. Theyl can be used by themselves or deposited or intimately mixed with carriers of acid, alkaline or neutral character, such as siliceous materials, porcelain, kieselguhr, pumice, silica-gel, natural or artificial zeoiites, alumina, bauxite, magnesia, slag, calcium'oxide or silicate, barium carbonate, active carbon and the like.

The eiliciency of the catalyst is very high, especially when used in very thin layers; therefore, even expensive catalysts can be used such as, e. g.. silver, platinum, palladium, rhodium, gold, beryllium and rhenium.

As the catalyst is maintained in a thin layer in a rather constant temperature, the requirements as to its mechanical strength can be neglected in favor of its activity; therefore, highly activated niya low. mechanical'rce., l

tions of dehydrogenation or Y For example, ethane, propane,butanes Y Vllarhocarbons can be converted either alone arneter producing about three t...

oi water gas daily. Relatively larse diameter is.

can lie-useful though Most oi the `catalysts refe to arel either m the water-gas rotion or in r with additions of steam or carbon diomde into ,Us :1i ures containing large proportions ot ce: tu ted hydrocarbons, which subsequently be use in polymerizlng them into liquid niotorfuels. In case of reactions producing dets oi carbon on the trays or causing a poisoning of the catalyst, the operation can be y. inter= rupted and steam or air or their -tures can passed to revivify the catalyst.

i 3fshows diagrammaticaily example oi a large unit of the preferred f-f' for conversionoi natural gas with ste into water-sas.

s unit is composed of two cylincal ap tus, each about feet high d i0 feet in on cubic ieet desirable since the capacity increases more than' proportionally to the diameter. In the annular reaction spaces I1 granular iron ore is used as a Icatalyst and is distributed in thin layers on trays. The annular reaction space is divided by perfo rated trays into annular compartments averaging about 3% inches high and 6 inches wide. The

catalyst layers yare about te inch thick, thus leaving an empty space about 3 inches high and 6 inches wide for distribution ofthe radiant heat. Natural gas and steam enter the reaction spaces through conduits I8 in regulated amounts and are forced through the catalyst layers, where the reaction takes place. Water-gas leaves the reaction chambers through conduits it. The heat "f necessary -for the reaction is furnished by radiation from or through the inner jackets 20 of cylindricai form `built of heat-resistant steel and suspended from the top (mechanical details of suspensiomnot shown, may be according to accepted engineering practice).

Jackets '20 are heated by combustion gases of gas burners 2 i to approximately i000 C. Though the temperatures of the Jackets might not be entirely uniform, some degree of auto-regulation of the temperature of the catalyst, due to the diierentrates of endo-thermic reaction at diilerent temperature levels, may be noticeable; Thus overheating at` any point may result in increased reaction velocity, which, due to its endothermic nature, will absorb more heat from the wall. i

Additional burners 22 are provided in the channel 2l through which combustion gases pass from the' first generator into the second. After i passing the second generator, the combustion gases serve to superheat the steam or other feed' gases in the preheater 24 and to generate steam in the boiler 2-5. The heat from the jackets 20 radiates either directly on the catalyst or by reflexion from the insulated outer wall 26.

The temperature of the catalyst in this speciiic example is approximately 800 C. For the temperature of thejacket of i000 C. and' of the catalyst of 800? C. the radiant heat transfer is of the order of 260 Ca1./m.1C-h. The llame temperature within the jacket may be of the order of -1100-1500 C.

Theexpansions and contractions 'of the jack/- l-ets can regulate automatically the amount of fuel and consequently the temperature of the process..

'ateniese Y e'. s. 300' C. to 126i!" i?. and of resist pressures 'of various inten ities,

. d and the various reactions. e. @the dehyrogenation process, can be coriciucterha if adveous or necery, under such temperatures and pressures. Annone 'the own means ot relatore or oi incr the `resistance oi the ifs against pressures, a suitable method is the weld ing of the catalyst trays to the heating jacket.

It will be understood that the various apparatus and processes described are merely representative examples and that this, invention is not described; it he observed that certain features and subwombinations are of utility t .1

may be employed without reference to other fea. tures and sub--combinationa- This is fr e -I plated by. and iswithin the scope of the inven tion.

What I cl is: l. A process ior carrying on an endo-thee vcatalytic reaction whichV comprises establishing at radiation, irradlating with said heat the catalytic surfaces oi spaced layers of catalyst arranged se in a coed space adjacent said predeteed space, and png the reactants in gaseous phase over the surfaces thus heated.

reaction which comprises ctcd capable of 0" to be limited to the speciic details shown and in s, preset@ ed space an incandescent source oi radiant heat adapted to supply the heat re i quirexnents oi the reaction predominantly by an endothermic i reactants in 3B a i f 1| ed ular space over catalytic 'suriaces oi a catalyst arranged in 'annular layers ced longitudinally of said conined space, burning viuei at incandescence within 'the central area dened by said annular conned space and ad- 40 jacent to the spaces between said layers and segregating the how of said reactants from the ow of products oi combustion from said burning fuel while radiating heat from said burning fuel.

onto said catalytic surfaces of said layers to supply the heat requirements reaction.

into chemical energy which comprises heating a thermal radiator to incandescence. a catalyst in spaced .permeable vlayers to radiant heat from said radiator, and passing through said layers in the areas thereof which are exposed to said radiant heat reactants which react endosaid catalyst, whereby the radiant heat received on the surface of the catalyst is converted by said reaction into chemical energy in the reaction products.` l

prises a reaction chamber provided with trays.

each provided with a' layer of catalyst and spaced thermically by catalytic action on the surface cf- 4. An apparatus for performing endothermic catalytic reactions in the gas phase which comof said-endothermic 3. The method of converting thermal energy I apart to leave a substantial free space over each with spaced periorate trayBLlayersotcataiyst on said trays, the spacing o! the trays being substantially wider than the thickness or said layers whereby to leave a substantial free space over each layer unobstructed for passage of radiant heat, an inner tubular wall of said chamber extending across the edges of said trays and said ree spaces and meansfor heating said wall to incandescence whereby to irradiate the surfaces of said layers through said free spaces, and thus to supply the heat requirements of theendothermic reaction predominantly by radiation.

6. An apparatus for performing endothermic catalytic reactions in the gas phase 'which ccmprises anVv annular reaction chamber provided with spaced perforate'trays, layers of catalyst 'on said trays. the spacing o! the trays being subheat, `an inner tubular -wall.ior said,chamber of a material which transmitsradiant heat,-ex tending across the edges of said trays and said free spaces, and aneinc'andescent source of radiant heat within the central space of said tubular wall whereby to irradiate the surfaces of said layers through said wall and said free spaces and thus to supply the heat requirements of the -endothermic'reaction predominantly by radia tion.

7. An apparatus as deined in claim 4 in which the means for producing -radiant heat is a fuel burner and a flue for leading products of combustion of said fuel consisting, at least in part, of said enclosing wall, and the trays are spaced more closely together nearer the hottest zone of said burner and farther apart as the distance from said hottest zone increases.

ROMAN WITKIEWICZ. 

